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CN113474284A - Parallel reforming in chemical plants - Google Patents

Parallel reforming in chemical plants Download PDF

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Publication number
CN113474284A
CN113474284A CN202080016582.6A CN202080016582A CN113474284A CN 113474284 A CN113474284 A CN 113474284A CN 202080016582 A CN202080016582 A CN 202080016582A CN 113474284 A CN113474284 A CN 113474284A
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gas
reforming reactor
reforming
reactor
steam methane
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P·M·莫滕森
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Topsoe AS
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Haldor Topsoe AS
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    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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Abstract

The invention relates to a chemical plant, comprising: -a reforming section arranged to receive a feed gas comprising hydrocarbons and to provide a combined synthesis gas stream, wherein the reforming section comprises: -an electrically heated reforming reactor containing a first catalyst, -an autothermal reforming reactor in parallel with the electrically heated reforming reactor, wherein the reforming section is arranged to output a combined synthesis gas stream comprising at least part of the first and/or second synthesis gas stream; -optionally a post-treatment unit downstream of the reforming section; -a gas separation unit arranged to separate the syngas stream into a water condensate and an intermediate syngas, and a downstream section arranged to receive the intermediate syngas and process the intermediate syngas into chemical products and off-gases. The invention also relates to a method for producing chemical products from a feed gas comprising hydrocarbons.

Description

Parallel reforming in chemical plants
Technical Field
The present invention relates to a chemical plant and a process for the production of chemical products by heterogeneous catalysis of a feed gas comprising hydrocarbons. The invention relates in particular to an apparatus and a method for producing synthesis gas, an apparatus and a method for producing methanol, an apparatus and a method for producing ammonia and an apparatus and a method for producing higher hydrocarbon mixtures.
Background
Autothermal reforming (ATR) based processes are routes to syngas production. The main elements of an ATR reactor are a burner, a combustion chamber and a catalyst bed housed within a refractory-lined pressure shell. In an ATR reactor, a sub-stoichiometric amount of oxygen partially combusts a hydrocarbon feed stream, and the partially combusted hydrocarbon feed stream is then steam reformed in a fixed bed of steam reforming catalyst. Due to the high temperature, a certain degree of steam reforming also takes place in the combustion chamber. The steam reforming reaction is accompanied by a water gas shift reaction. Typically, the gas is at or near equilibrium at the outlet of the reactor relative to the steam reforming and water gas shift reactions. The temperature of the outlet gas is typically between 850 ℃ and 1100 ℃. More details and a complete description of ATR can be found in the prior art, such as "students in Surface Science and Catalysis", Vol.152, "Synthesis gas production for FT Synthesis"; chapter 4, p.258-352,2004.
It is an object of the present invention to provide an alternative arrangement for a chemical plant for producing chemical products.
It is another object of the present invention to provide a system and method for producing syngas by reforming in which the overall energy consumption is reduced compared to systems having a single combustion reforming reactor, such as tubular steam methane reformers, autothermal reformers or convection reformers.
It is a further object of the present invention to provide an apparatus and method in which the capacity of an existing reforming reactor, such as a combustion reforming reactor or an autothermal reformer, can be increased.
It is a further object of the present invention to provide an apparatus and method that provides a high degree of flexibility in the composition of the syngas produced.
It is a further object of the present invention to provide a chemical plant and process in which carbon dioxide and other climate harmful emissions (e.g., NO) are reduced by minimizing the consumption of hydrocarbons that provide heat for the reforming reactionx、SOxEtc.) of the total emissions.
Disclosure of Invention
In the following, reference is made to embodiments of the invention. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. In contrast, any combination of the following features and elements, whether related to different embodiments or not, is contemplated to implement and practice the invention.
One aspect of the invention relates to a chemical plant comprising:
-a reforming section arranged to receive a feed gas comprising hydrocarbons and to provide a combined synthesis gas stream, wherein the reforming section comprises:
-an electrically heated reforming reactor containing a first catalyst, the electrically heated reforming reactor being arranged to receive a first portion of the feed gas and to produce a first synthesis gas stream,
-an autothermal reforming reactor in parallel with the electrically heated reforming reactor, the autothermal reforming reactor containing a second catalyst, the autothermal reforming reactor being arranged to receive a second portion of the feed gas and to output a second synthesis gas stream,
wherein the reforming section is arranged to output a combined syngas stream comprising at least a portion of the first and/or second syngas streams,
an optional post-treatment unit downstream of the reforming section, wherein the optional post-treatment unit is arranged to receive the combined syngas stream and to provide a post-treated syngas stream,
-a water separation unit arranged to separate the combined syngas stream or the post-treated syngas stream into a water condensate and an intermediate syngas, and
-a downstream section arranged to receive the intermediate syngas and process the intermediate syngas into chemical products and off-gas.
In some embodiments, all of the first and/or second syngas is output from the reforming section as a combined syngas stream; however, in other embodiments, only a portion of the first synthesis and/or all of some of the second synthesis (e.g., 20 vol% of the first and/or second syngas stream) is output as a combined syngas stream, while other portions thereof are output as syngas for other purposes.
In case it is desired to increase the total yield of syngas in the reforming section of a chemical plant, it is advantageous to supplement the autothermal reforming reactor with an electrically heated reforming reactor instead of, for example, a Steam Methane Reformer (SMR) or a gas heated reforming reactor (including a heat exchange reformer), if the only reforming reactor is the autothermal reforming reactor.
This is due at least to:
this combination provides lower cumulative carbon dioxide generation compared to the combination of an autothermal reforming reactor and SMR, particularly if the electricity to electrically heat the reforming reactor is from a renewable energy source,
carbon dioxide and other climatically harmful emissions (e.g. NO) by minimizing the amount of hydrocarbons used to provide heat for the reforming reactionxOr SOx) The total emission of (2) is significantly reduced;
electrically heating the reforming reactor makes it possible to output the first syngas at a higher temperature and/or at a higher pressure than is possible for the SMR, thereby ensuring the methane content of the first syngas and, consequently, the methane content of the combined syngas can be reduced;
the pressure of the combined synthesis gas can be higher, in particular because the SMR is limited to a maximum pressure of about 25barg, compared to autothermal reforming and electrically heated reforming, both of which can operate at pressures in excess of 30barg, more preferably in excess of 40 barg;
The operating conditions of the gas-heated reforming reactor are limited to high steam-to-carbon ratios to avoid metal dusting, which is not the case with the electrically heated reforming reactor;
the electrically heated reforming reactor is significantly smaller in size than the SMR or gas heated reforming reactor and therefore easier to implement into existing compartments;
the H of the combined synthesis gas output from the reforming section can be adjusted by controlling the amount of the first portion of feed gas entering the electrically heated reforming reactor and the amount of the second portion of feed gas entering the autothermal reforming reactor2the/CO ratio, thereby indirectly controlling oxygen consumption;
furthermore, the modulus M of the post-treated syngas stream can be adjusted. The modulus M is the stoichiometric ratio (H)2-CO2)/(CO+CO2). The modulus M can be adjusted to be between about 1.8 and 2.2, more preferably about 2.0 or 2.1, which can be used in the case where the downstream section comprises a methanol reactor arranged to convert the intermediate synthesis gas to methanol.
In more detail, the technical advantages of the device of the invention can be explained as follows: ATR typically produces an output gas at a temperature of 1000 ℃ or more and a pressure of up to 45 barg. Conventional SMR and gas heated reformers produce output gas at a temperature of about 850 ℃ and a pressure of 25 to 30 barg. Because of mechanical limitations, SMRs are typically excluded from operation at higher pressures, and gas heated reformers are excluded from operation at higher pressures, because the conversion of methane is disadvantageously reduced at the highest temperatures involved. Overall, this means that methane conversion in the SMR and gas heated reformer will be relatively low because the outlet temperature is relatively low and when mixed with the output gas of the SMR or gas heated reformer, the result is an increase in the methane content of the gas and, correspondingly, an increase in the methane content of the combined syngas. Furthermore, the pressure limitations of an SMR or gas heated reformer mean that when the output gas of the ATR is mixed with the output gas of a conventional SMR or gas heated reformer, the pressure of the gas output from the ATR must be reduced to the same level as the pressure of the output gas from the conventional SMR or gas heated reformer. The reduced pressure of the combined synthesis gas means that the requirements for downstream compression of the combined synthesis gas will increase, since many applications of synthesis gas, such as methanol synthesis (typically above 70 bar), require high pressures. The invention is based on the following recognition: the output gas may be produced from an electrically heated steam methane reformer having the same elevated temperature and pressure as the output gas from the ATR, thus avoiding said pressure reduction of the output gas from the ATR, thereby producing a combined syngas of reduced methane content. Thus, it has surprisingly been found that in an electrically heated steam methane reformer, an output gas can be produced having a temperature of up to about 1100 or more and a pressure of up to 100 barg.
In addition to the second portion of the feed gas to the autothermal reforming reactor, a stream of oxidant gas is also introduced. The oxidant gas stream comprises oxygen and may be, for example, air or oxygen, or a mixture in which more than 90% is oxygen, with the balance being, for example, nitrogen, steam and/or argon.
It should be noted that the first, second and optional third portion of the hydrocarbon-containing feed gas may be a first, second and optional third portion of a single hydrocarbon-containing feed gas stream, wherein the single feed gas stream is divided into a plurality of streams that may be fed together with steam to the first, second and optional third reforming reactors. In this case, the composition of the first, second and optionally third portions of the feed gas is substantially the same. However, additional gases (e.g., oxidant gas and/or steam) may be added to the first, second and optional third portions of the feed gas before they are fed to the respective reforming reactors. The term "feed gas" received by the reforming section is intended to mean the total amount of feed gas fed to the reforming reactor, although the first, second and optional third feed gases may be fed separately to the reforming reactor of the reforming section. Thus, when the reforming section comprises an electrically heated reforming reactor receiving a first portion of the feed gas and an autothermal reforming reactor receiving a second portion of the feed gas, the term "feed gas" is intended to mean the total feed gas comprising the first and second portions of the feed gas. Similarly, when the reforming section comprises an electrically heated reforming reactor receiving a first portion of the feed gas, an autothermal reforming reactor receiving a second portion of the feed gas, and a gas heated reforming reactor receiving a third portion of the feed gas, the term "feed gas" refers to the total feed gas comprising the first, second and third portions of the feed gas.
The chemical equipment of the inventionThe combined syngas production of the reforming section is increased. An alternative method of increasing the reforming section throughput is to combine a steam fired methane reformer with an autothermal reforming reactor or an autothermal reforming reactor with a heat exchange reforming reactor. The combination of an electrically heated reforming reactor and an autothermal reforming reactor is preferred over the combination of a steam fired methane reforming reactor and an autothermal reforming reactor because of the reduction in total CO2And is discharged and due to the combined syngas having a higher temperature and/or pressure than the previous combination. Furthermore, the combination of an electrically heated reforming reactor and an autothermal reforming reactor is preferred over the combination of an autothermal reforming reactor and a heat exchange reforming reactor because heat exchange reforming reactors are limited to operation at high steam to carbon ratios to avoid metal dusting problems.
The chemical plant of the present invention provides the concept of obtaining synergy between the operation of an electrically heated reforming reactor and an autothermal reforming reactor. By placing the electrically heated reforming reactor in parallel with the autothermal reforming reactor, both reforming reactors can share the same preheating and pretreatment systems or portions thereof. Furthermore, by having the partial reforming reaction take place in an electrically heated reforming reactor, the input of hydrocarbons providing heat for the steam reforming reaction is reduced compared to using a steam methane reforming reactor in parallel with an autothermal reforming reactor. Thus, for a given output of combined syngas from the reforming section, the overall consumption of hydrocarbons is minimized.
Furthermore, by combining an autothermal reforming reactor and an electrically heated reforming reactor, the composition of the synthesis gas exiting the reforming section can be controlled. This is particularly useful if the downstream section is, for example, a methanol synthesis section.
The capacity of existing chemical plants with autothermal reforming reactors can be increased by adding electrically heated reforming reactors, and the use of hydrocarbons for the heating side of the reforming section is rarely, if ever, increased, as the power for the electrically heated reforming reactors can be supplied from renewable sources such as wind energy. Furthermore, since the electrically heated reforming reactor is a very compact reactor, it can be installed generally on the same land as existing chemical plants.
The downstream section may for example be a cold box, a pressure swing adsorption unit, a methanol synthesis section, an ammonia section or a fischer-tropsch section. Other downstream stages are also possible, such as downstream stages for acetic acid production or DME production.
In fired tubular steam methane reformers, heat transfer by convection and/or radiant heating can be slow and often encounters significant resistance. The innermost temperature of the tubes of a fired tubular steam methane reformer is slightly lower than the outside temperature of the tubes due to the rate of heat transfer through the walls of the tubes and to the catalyst within the tubes and due to the endothermic nature of the steam reforming reaction. In an electrically heated reforming reactor, the maximum temperature may be obtained near the first catalyst. Thus, by using electrical heating, the burning of the high temperature flue gas of the steam methane reformer is avoided, and therefore less energy is required in the reforming section of the electrically heated reactor. In addition, by minimizing the amount of hydrocarbons used to provide heat for the reforming reaction, carbon dioxide and other climate harmful emissions (e.g., NO) are reduced xOr SOx) Total emission of (c).
Furthermore, if the power for heating the electrically heated reforming reactor and other possible units of the chemical plant is provided by renewable energy sources, the total consumption of hydrocarbons for the chemical plant will be minimized, CO2The amount of emissions is reduced accordingly.
Typically, the combined syngas stream from the reforming section comprises the first and second syngas streams. Thus, further processing of the combined syngas stream from the reforming section is used in combination in all of the first and second syngas streams. However, it is envisioned that the combined syngas stream contains only a portion of the first and/or second syngas streams and that the remaining syngas stream is directed to other equipment downstream of the reforming section. This may be the case, for example, where the chemical plant is arranged to provide the chemical product in the form of one hydrogen stream and another CO-rich synthesis gas stream.
In the context of the present application, the term "hydrocarbon-containing feed gas" is intended to mean a gas having one or more hydrocarbons and possibly other constituents. Generally, therefore, in addition to small amounts of other gases,the feed gas comprising hydrocarbons comprises a hydrocarbon gas, e.g. CH4And optionally, generally relatively small amounts of higher hydrocarbons. Higher hydrocarbons are components having two or more carbon atoms, such as ethane and propane. Examples of "hydrocarbon gases" may be natural gas, LPG, town gas, biogas, naphtha or a mixture of methane and higher hydrocarbons. Hydrocarbons may also be components having atoms other than carbon and hydrogen, such as oxygenates. The term "feed gas comprising hydrocarbons" refers to a feed gas comprising a hydrocarbon gas in which one or more hydrocarbons are mixed with steam, hydrogen and possibly other components such as carbon monoxide, carbon dioxide and nitrogen and argon. Typically, the feed gas to the reforming section has a predetermined ratio of hydrocarbon gas, steam and hydrogen, and possibly carbon dioxide. It should be noted that a feed gas comprising purified (e.g. desulphurised and/or pre-reformed) hydrocarbons is still considered to be a feed gas comprising hydrocarbons.
Further, the term "steam reforming" or "steam methane reforming reaction" refers to a reforming reaction that proceeds according to one or more of the following reactions:
Figure BDA0003228655380000061
Figure BDA0003228655380000062
Figure BDA0003228655380000063
reactions (i) and (ii) are steam methane reforming reactions, while reaction (iii) is a dry methane reforming reaction.
For higher hydrocarbons, i.e. CnHmWherein n is greater than or equal to 2 and m is greater than or equal to 4, formula (i) is summarized as:
Figure BDA0003228655380000064
wherein n is more than or equal to 2, m is more than or equal to 4
Typically, steam reforming is accompanied by the water gas shift reaction (v):
Figure BDA0003228655380000071
the terms "steam methane reforming" and "steam methane reforming reaction" are meant to cover reactions (i) and (ii), the term "steam reforming" is meant to cover reactions (i), (ii) and (iv), and the term "methanation" covers the reverse of reaction (i). In most cases, all of these reactions (i) - (v) are at or near equilibrium at the outlet of the reforming reactor. The term "prereforming" is generally used to cover the catalytic conversion of higher hydrocarbons according to reaction (iv). Prereforming is typically accompanied by steam reforming and/or methanation (depending on gas composition and operating conditions) and water gas shift reactions. Prereforming is usually carried out in an adiabatic reactor, but can also be carried out in a heated reactor.
In the case of autothermal reforming, steam methane reforming is preceded by a reaction zone in which combustion and partial combustion of the feedstock takes place.
Furthermore, in addition to the steam methane reforming reaction, the terms "autothermal reforming" and "autothermal reforming reaction" also encompass the combustion and partial combustion of the hydrocarbon feedstock according to reactions (vi) and (vii):
Figure BDA0003228655380000072
Figure BDA0003228655380000073
the term "synthesis gas" refers to a gas comprising hydrogen, carbon monoxide and also carbon dioxide and small amounts of other gases such as argon, nitrogen, methane and the like.
Typically, the feed gas will undergo desulfurization to remove sulfur therefrom prior to entering the reforming section, thereby avoiding catalyst deactivation in the process.
In one embodiment, the chemical plant further comprises a gas purification unit and/or a pre-reforming unit upstream of the reforming section. The gas cleaning unit is, for example, a desulfurization unit, such as a hydrodesulfurization unit.
In the prereformer the hydrocarbon gas will be prereformed according to reaction (iv) together with steam and possibly also hydrogen and/or other components such as carbon dioxide at a temperature range of about 350-550 ℃ to convert higher hydrocarbons as an initial step of the process, which usually takes place downstream of the desulfurization step. This eliminates the risk of carbon formation from higher hydrocarbons on the catalyst in subsequent process steps. Optionally, carbon dioxide or other components may also be mixed with the gas exiting the pre-reforming step to form the feed gas.
In one embodiment, the water separation unit of the chemical plant is a flash separation unit, typically preceded by a suitable temperature reduction device. Flash separation refers to a phase separation unit in which, at a given temperature, a stream is separated into a liquid phase and a vapor phase that are near or at thermodynamic phase equilibrium.
In one embodiment, an electrically heated reforming reactor of a chemical plant comprises:
a pressure shell containing an electrical heating unit arranged to heat the first catalyst, wherein the first catalyst comprises a catalytically active material operable to catalyze the steam reforming of the first feed gas, wherein the pressure shell has a design pressure of between 5 and 45 bar, preferably between 30 and 45 bar,
-an insulating layer adjacent to at least a portion of the interior of the pressure shell, and
at least two conductors electrically connected to the electrical heating unit and to a power source placed outside the pressure shell,
wherein the power source is dimensioned to heat at least a portion of the first catalyst to a temperature of at least 800 ℃, preferably at least 950 ℃, or even more preferably at least 1050 ℃, by passing an electric current through the electrical heating unit.
An important feature of an electrically heated reforming reactor is that energy is provided internally within the reforming reactor, rather than by external heat sources such as heat conduction, convection, and radiation, for example, through catalyst tubes. In an electrically heated reforming reactor having an electrical heating unit connected to a power source by a conductor, heat for the steam reforming reaction is provided by resistance heating. The hottest part of the electrically heated reforming reactor will be located within the pressure shell of the electrically heated reforming reactor. Preferably, the power supply and the electrical heating unit within the pressure shell are dimensioned such that at least a part of the electrical heating unit reaches a temperature of 850 ℃, preferably 900 ℃, more preferably 1000 ℃ or even more preferably 1100 ℃.
The chemical plant of the invention may advantageously comprise one or more compressors and/or pumps upstream of the reforming section. The compressor/pump is arranged to compress the feed to a pressure of between 5 and 45 bar, preferably between 30 and 45 bar. The components of the feed, i.e., water/steam, hydrogen, and hydrocarbon feed gas, may be separately compressed and separately fed to the reforming section or reforming reactor thereof.
The first catalyst may be a bed of catalyst particles (e.g. pellets), typically in the form of a catalytically active material supported on a high area support, with electrically conductive structures embedded in the bed of catalyst particles. Alternatively, the first catalyst may be a catalytically active material supported on a macrostructure (e.g., a monolith).
When the electrically heated reforming reactor comprises an insulating layer adjacent to at least a portion of the interior of the pressure shell, a suitable thermal and electrical insulation is obtained between the electrical heating unit and the pressure shell. Typically, an insulating layer will be present at most of the interior of the pressure shell to provide thermal insulation between the pressure shell and the electrical heating unit/first catalyst; however, channels in the insulation layer are required to provide connections for conductors between the electrical heating units and the power supply and to provide inlets/outlets for gases to/from the electrically heated reforming reactor.
The presence of an insulating layer between the pressure shell and the electrical heating unit helps to avoid overheating of the pressure shell and helps to reduce heat loss around the electrically heated reforming reactor. The temperature of the electrical heating unit, at least in some parts thereof, may reach about 1300 ℃, but by using a heat insulating layer between the electrical heating unit and the pressure shell, the temperature of the pressure shell may be kept at a significantly lower temperature, e.g. 500 ℃ or even 200 ℃. This is advantageous because conventional construction steels are not suitable for applications that are subjected to stresses at high temperatures (e.g. above 1000 ℃). Furthermore, the thermal insulation layer between the pressure shell and the electrical heating unit helps to control the current flow within the reforming reactor, since the thermal insulation layer is also electrically insulating. The insulating layer may be one or more layers of solid material such as ceramic, inert material, refractory material, or gas barrier layer, or a combination thereof. It is therefore also conceivable that the purge gas or the confined gas constitutes or forms part of the thermal insulation layer.
Since the hottest part of the electrically heated reforming reactor during operation is the electrically heated unit and since the insulating layer insulates the pressure shell from the electrically heated reforming reactor, the temperature of the pressure shell can be kept significantly below the maximum process temperature. This allows the pressure shell to have a relatively low design temperature, for example a pressure shell of 700 ℃ or 500 ℃ or preferably 300 ℃ or 200 ℃, while having a maximum process temperature of 900 ℃ or even 1100 ℃ or even up to 1300 ℃.
Another advantage is that the lower design temperature compared to the fired SMR means that the thickness of the pressure shell can be reduced in some cases, thereby saving cost.
It should be noted that the term "thermally insulating material" is intended to mean a material having a thickness of about 10 W.m-1·K-1Or a material of lower thermal conductivity. Examples of thermally insulating materials are ceramics, refractory materials, alumina-based materials, zirconia-based materials, and the like.
In one embodiment, the electrical heating unit comprises a macrostructure of electrically conductive material, wherein the macrostructure supports the ceramic coating and the ceramic coating supports the catalytically active material of the first catalyst. Thus, during operation of the chemical plant, an electric current passes through the macrostructures and thereby heats the macrostructures and the catalytically active material supported thereon. The close proximity between the catalytically active material and the macrostructures enables efficient heating of the catalytically active material by solid material thermal conduction from the resistively heated macrostructures. Under given operating conditions, the amount and composition of the catalytically active material may be adjusted according to the steam reforming reaction. The surface area of the macrostructures, the proportion of macrostructures coated with ceramic coating, the type and structure of the ceramic coating, and the amount and composition of catalytically active material can be adjusted according to the steam reforming reaction under given operating conditions.
The term "electrically conductive" means having a resistivity of 10 at 20 deg.C-4To 10-8Omega · m material. Thus, the electrically conductive material is, for example, a metal, such as copper, silver, aluminum, chromium, iron, nickel, or a metal alloy. Furthermore, the term "electrically insulating" means having a resistivity higher than 10 Ω · m at 20 ℃, for example 10 at 20 ℃9To 1025Omega · m material.
As used herein, the term "electrically heated unit containing a macroscopic catalyst" is not meant to be limited to reforming reactors having a single macroscopic structure. Rather, the term is intended to encompass macrostructures having a ceramic coating and a catalytically active material supported thereon, as well as a series of such macrostructures having a ceramic coating and a catalytic material supported thereon.
The term "macrostructures supporting a ceramic coating" is intended to mean that the macrostructures are coated with the ceramic coating at least a portion of the surface of the macrostructures. Thus, the term does not imply that all surfaces of the macrostructures are covered by the ceramic coating; in particular, there is no coating at least on the portion of the macrostructure that is electrically connected to the conductor and thus to the power source. The coating is a ceramic material with pores in its structure, which can support the catalytically active material of the first catalyst on and inside the coating and which has the same function as the catalytic carrier. Advantageously, the catalytically active material of the first catalyst comprises catalytically active particles having a size in the range of from about 5nm to about 250 nm.
As used herein, the term "macrostructure" is intended to mean a structure that is large enough to be visible to the naked eye without the need for magnification means. The dimensions of the macrostructures are generally in the range of centimeters or even meters. The dimensions of the macrostructures are advantageously at least partially adapted to the internal dimensions of the pressure shell, so that space is saved for the thermal insulation and the conductors.
The ceramic coating, with or without catalytically active material, may be added directly to the metal surface by wash coating. The wash coating of metal surfaces is a well known process; described in, for example, Cybutski, A., and Moulijn, J.A., Structured catalysts and acts, Marcel Dekker, Inc, New York,1998, Chapter 3, and references therein. A ceramic coating may be added to the surface of the macrostructures, followed by the addition of a catalytically active material; alternatively, a ceramic coating comprising a catalytically active material is added to the macrostructure.
Preferably, the macrostructures are produced by extruding a mixture of powder metal particles and binder into an extruded structure and then sintering the extruded structure to provide a material having a high geometric surface area per unit volume. To form a chemical bond between the ceramic coating and the macrostructures, a ceramic coating that may include a catalytic material is provided on the macrostructures prior to a second sintering in an oxidizing atmosphere. Alternatively, the catalytically active material may be impregnated onto the ceramic coating after the second sintering. When a chemical bond is formed between the ceramic coating and the macrostructure, a particularly high thermal conductivity between the electrically heated macrostructure and the catalytically active material supported by the ceramic coating is possible. Due to the close distance between the heat source, i.e. the macrostructure, and the catalytically active material, the heat transfer is efficient, so that the catalytically active material can be heated very efficiently. Thus, a compact reforming reactor is possible in terms of gas handling per unit volume of reforming reactor, and thus a reforming reactor accommodating macrostructures may be compact. The reforming reactor of the present invention does not require a furnace and this significantly reduces the size of the electrically heated reforming reactor.
In another embodiment, the macro-mixture is manufactured by 3D printing and/or additive manufacturing.
Preferably, the macrostructures comprise Fe, Ni, Cu, Co, Cr, Al, Si, or alloys thereof. Such alloys may include other elements, such as Mn, Y, Zr, C, Co, Mo, or combinations thereof. Preferably, the catalytically active material of the first catalyst is particles having a size of 5nm to 250 nm. The catalytically active material of the first catalyst may for example comprise nickel, ruthenium, rhodium, iridium, platinum, cobalt or combinations thereof. One possible catalytically active material of the first catalyst is therefore a combination of nickel and rhodium and another combination of nickel and iridium. The ceramic coating may for example be an oxide comprising Al, Zr, Mg, Ce and/or Ca. Exemplary coatings are calcium aluminate or magnesium aluminate spinels. Such ceramic coatings may comprise additional elements, such as La, Y, Ti, K, or combinations thereof. Preferably, the conductors are made of a material different from the macrostructures. The conductor may be, for example, iron, nickel, aluminum, copper, silver, or alloys thereof. The ceramic coating is an electrically insulating material and is typically around 100 μm thick, for example 10-500 μm thick. Additionally, a sixth catalyst may be placed in the channels within the pressure shell and within the macrostructures, around or upstream of the macrostructures, and/or upstream of the macrostructures to support the catalytic function of the macrostructures.
In an embodiment, the chemical plant further comprises a control system arranged to control the power supply to ensure that the temperature of the gas leaving the electrically heated reforming reactor is within a predetermined range and/or to ensure that the conversion of hydrocarbons in the first portion of the feed gas is within a predetermined range and/or to ensure that the dry molar concentration of methane is within a predetermined range and/or to ensure that the approach equilibrium of the steam reforming reaction is within a predetermined range. Typically, the maximum temperature of the gas within the electrically heated reforming reactor is between 800 ℃ and 1000 ℃, such as between 850 ℃ and 1000 ℃, for example at about 950 ℃, but even higher temperatures are conceivable, such as up to 1300 ℃. The highest temperature of the first syngas, as seen in the flow direction of the first portion of the feed gas, will be achieved close to the most downstream portion of the first catalyst.
The control of the power supply is the control of the electrical output of the power supply. The control of the power supply may be performed, for example, as a control of the voltage and/or current from the power supply, as a control of whether the power supply is switched on or off, or a combination thereof. The power supplied to the electrical heating unit of the first catalyst may be in the form of alternating current or direct current.
In one embodiment, the chemical plant further comprises a fired heater unit upstream of the autothermal reforming reactor (ATR reactor) and optionally means for recycling at least part of the off-gas from the downstream section as fuel to the fired heater unit, wherein the fired heater unit is arranged to preheat the second portion of the feed gas.
By recycling the off-gas from the downstream section back to the fired heater unit, it is possible to maximise the use of hydrocarbons in the feed to the process side and minimise the use of hydrocarbons in the fired heater unit. The chemical plant may be balanced such that the operation of the combustion heating unit is adjusted to be driven mainly or even completely by the heat supplied by combusting the recirculated exhaust gas. This allows for minimal use of the incoming natural gas in the chemical plant to burn the heat supply, which in turn allows for optimal utilization of the hydrocarbon-containing feed gas incoming to the chemical plant. Typically, a relatively small amount of make-up gas comprising hydrocarbons is also fed to the combustion heating unit to allow control of the load of the combustion heating unit. The term "load" is understood herein as the heat input added or removed in a unit operation of a chemical plant.
In an embodiment, the reforming section further comprises a fired steam methane reforming reactor upstream of the autothermal reforming reactor, wherein the fired steam methane reforming reactor comprises one or more tubes containing a third catalyst, wherein the fired steam methane reforming reactor comprises one or more burners for providing heat for the steam methane reforming reaction within the one or more tubes, and wherein the chemical plant comprises means for recycling at least part of the exhaust gas from the downstream section as fuel to the one or more burners of the fired steam methane reforming reactor, wherein the fired steam methane reforming reactor is arranged to receive a second portion of the feed gas and to provide a partially reformed second feed gas, and wherein the partially reformed second feed gas is directed to the autothermal reforming reactor.
A typical fired steam methane reforming reactor has a plurality of tubes placed within a furnace, which are filled with catalyst pellets. The tubes are typically 10-13 metres long and typically have an internal diameter of between 80 and 160 mm. Burners placed in the furnace provide the necessary heat for the reaction by combustion of the fuel gas.
The fuel gas for these combustion processes is typically a mixture of exhaust gas from processes downstream of the reformer and imported natural gas or other suitable hydrocarbon.
Since the temperature of the partially reformed second feed gas exiting the fired steam methane reforming reactor may be relatively high, for example 700 ℃ to 900 ℃, the second portion of the feed gas need not be preheated in a separate fired heater unit before being introduced into the autothermal reforming reactor.
In one embodiment, the reforming section of the chemical plant further comprises a gas-heated steam methane reforming reactor in parallel with the combination of the electrically heated reforming reactor and the autothermal reforming reactor. The gas heated steam methane reforming reactor contains a fourth catalyst and is operable to receive a third portion of the feed gas and utilize at least a portion of the first and/or second syngas stream as a heating medium for heat exchange within the gas heated steam methane reforming reactor. The gas heated steam methane reforming reactor is arranged to produce a third synthesis gas stream over a fourth catalyst and for outputting the third synthesis gas stream from the reforming section as at least a portion of the combined synthesis gas. The addition of a gas heated steam methane reforming reactor increases the overall thermal efficiency of the chemical plant because of the use of the sensible heat of the first and second synthesis gas streams within the gas heated steam methane reforming reactor. Furthermore, when the chemical plant includes a gas heated steam methane reforming reactor, the overall yield of the chemical plant is increased.
The gas heated steam methane reforming reactor is configured to provide heat for the endothermic steam methane reforming reaction by heat exchange using hot gases, typically on the tube walls. One example of a configuration of a heat exchange reformer has a plurality of catalyst-filled parallel tubes that receive a feed gas. At the bottom of the reactor, the product gas from the catalyst-filled tubes is mixed with hot syngas from the upstream reforming unit, and the combined syngas is heat exchanged with the catalyst-filled tubes. Other configurations of heat exchange reforming are also contemplated.
Reducing metal dusting in heat exchange reforming reactors
In one embodiment, the reforming section further comprises a gas-heated steam methane reforming reactor upstream of the autothermal reforming reactor, wherein the gas-heated steam methane reforming reactor contains a fourth catalyst and is operable to utilise at least part of the second synthesis gas stream as a heating medium for heat exchange within the gas-heated steam methane reforming reactor, the gas-heated steam methane reforming reactor being arranged to receive the second portion of the feed gas and to provide a partially reformed second feed gas, wherein the partially reformed second feed gas is introduced into the autothermal reforming reactor. In a particular embodiment, the gas-heated steam methane reforming reactor is further operable to utilize at least a portion of the first syngas stream as a heating medium for heat exchange within the gas-heated steam methane reforming reactor.
By adding a gas heated steam methane reforming reactor, the overall thermal efficiency of the chemical plant is increased because the sensible heat of the first and second syngas streams is used in the gas heated steam methane reforming reactor. Furthermore, when the chemical plant includes a gas heated steam methane reforming reactor, the overall yield of the chemical plant is increased. Gas heated steam methane reforming reactors in the form of heat exchange reformers have the inherent technical problem of metal dusting, i.e. corrosion of the metal surfaces of the reactor when exposed to carbon monoxide rich gases. Metal dusting can be described by the following reaction:
Figure BDA0003228655380000141
it has surprisingly been found that the level of metal dusting in the heat exchange is greatly reduced when an electrically heated reforming reactor is added in parallel with the combination of a heat exchange reformer and an autothermal reforming reactor. Without being bound by theory, it is believed that this is due to the reduced temperature difference between the equilibrium temperature of reaction (viii) and the outlet temperature of the second syngas after cooling in the heat exchange reformer. The temperature of the second syngas exiting the heat exchange reformer is higher than when the electrical reformer is not included.
Further advantages of the above embodiments include:
The load required for the heat exchange reformer is reduced, i.e. the size of the reformer is reduced.
The electrically heated reforming reactor is a very compact reactor compared to combustion reactors and steam reformers, thus reducing the footprint of the reactor.
Electrically heated reforming reactors offer the possibility of operating the reactor using only sustainable energy, thus minimizing CO2And (5) discharging.
In a particular embodiment, the first portion of the feed gas is less than 25 volume percent of the total feed gas, preferably less than 20 volume percent, more preferably less than 15 volume percent.
In a particular embodiment, the load transferred in the electrically heated reforming reactor is less than 40%, preferably less than 30%, more preferably less than 20% of the total load transferred in the electrically heated reforming reactor and the gas heated steam methane reforming reactor.
In a particular embodiment, the temperature of the second synthesis gas leaving the gas heated steam methane reforming reactor is above 600 ℃, preferably above 650 ℃, more preferably above 700 ℃.
In a particular embodiment, the difference between the equilibrium temperature of reaction (viii) and the outlet temperature of the second syngas after cooling in the heat exchange reformer is less than 250 ℃, preferably less than 150 ℃, and more preferably less than 75 ℃.
The equilibrium temperature for reaction (viii) can be obtained by initially calculating the quotient (Q) for a given gas as follows:
Figure BDA0003228655380000151
where y isjIs the mole fraction of compound j and P is the total pressure in bar. This is used to determine the equilibrium temperature (T) at which a given quotient of reactants equals the equilibrium constanteq)：
Q＝KCOred(Teq)
Where Kcored is the thermodynamic equilibrium constant of reaction (viii). The equilibrium temperature (. DELTA.T) of reaction (viii) is then setapp，COred) Is defined as:
ΔTapp，COred＝Teq-T
where T is the bulk temperature of the gas.
In one embodiment, the feed gas is desulfurized and adiabatically prereformed prior to being divided into the first and second portions of the feed gas. In one embodiment of the invention, steam is added to the first portion of the feed gas. In one embodiment of the invention, steam is added to the second portion of the feed gas. In one embodiment of the invention, steam is added to both the first and second portions of the feed gas. In one embodiment of the invention, the first portion and the second portion of the feed gas have the same composition. In a particular embodiment of the invention, the first portion and the second portion of the feed gas have different compositions.
In a particular embodiment, the process of the present invention relates to a process wherein the reforming section further comprises a gas heated steam methane reforming reactor located upstream of the autothermal reforming reactor, wherein the gas heated steam methane reforming reactor comprises a fourth catalyst, the process further comprising the steps of:
-introducing said second portion of feed gas into said gas heated steam methane reforming reactor and performing steam methane reforming within said combustion reforming reactor to provide a partially reformed second feed gas,
-providing the partially reformed second feed gas to the autothermal reforming reactor, and
-using at least part of the first and/or second synthesis gas stream as a heating medium for heat exchange in the gas heated steam methane reforming reactor.
A particular embodiment of the method of the previous paragraph further comprises the steps of:
utilizing at least a portion of the first syngas stream as a heating medium for heat exchange within the gas-heated steam methane reforming reactor.
Further embodiments
In one embodiment, the post-treatment unit is a post-conversion unit having an inlet that allows heated CO to be introduced2Added to the combined synthesis gas upstream of the post-conversion unit. The post-treatment unit contains a fifth catalyst for catalyzing steam methane reforming, methanation, and reverse water gas shift reactions. The post-conversion unit is for example an adiabatic post-conversion device or a gas heat exchange reactor. The post-treatment synthesis gas stream is H 2The ratio of/CO is lower than the H of the combined synthesis gas2Syngas stream with/CO ratio. By adding heated CO in a separate reactor downstream of the reforming section2Performing steam methane reforming, methanation and reverse water gas shift reactions, the CO production of the process can be increased and/or H can be adjusted2The ratio of/CO. Post-treating H of a syngas stream2the/CO ratio is for example below 1.8, below 1.5 or even below 1.0. Added heated CO2May be, for example, about 300 ℃, 400 ℃ or even about 500 ℃ or higher.
In one embodiment, the post-treatment unit is a water gas shift unit arranged to perform a water gas shift reaction. In this embodiment, the intermediate syngas (i.e., the post-treated syngas) is a water-gas shifted syngas stream, such as a hydrogen-rich syngas or hydrogen stream. The water gas shift unit may be a single water gas shift unit, such as a medium temperature water gas shift unit, or a combination of two or more water gas shift units (e.g., a high temperature water gas shift unit and a low temperature water gas shift unit).
In one embodiment, the downstream section comprises a gas separation unit arranged to separate substantially pure CO2、H2And/or a stream of CO is separated from the syngas inlet to the downstream section, thereby providing a refined syngas.
Here, the term "refined synthesis gas" refers to the selective separation of CO, CO in a gas2Or H2Or selective gas separation of CO2And CO or H2Followed by synthesis gas obtained from the intermediate synthesis gas. The gas separation unit comprises one or more of the following units: CO 22A removal unit, a pressure swing adsorption unit, a membrane, and/or a cryogenic separation unit. CO 22Removal refers to the removal of CO from process gases using processes such as chemisorption2The unit (2). In chemisorption, the CO is included2With CO2Solvents that react and are combined in this way. Most chemical solvents are amines, classified as primary amines such as Monoethanolamine (MEA) and Diglycolamine (DGA), secondary amines such as Diethanolamine (DEA) and Diisopropanolamine (DIPA), or tertiary amines such as Triethanolamine (TEA) and Methyldiethanolamine (MDEA), although ammonia and liquid alkali metal carbonates, such as K2CO3And NaCO3. Swing adsorption refers to a unit for adsorbing a selected compound. In this type of device, a dynamic equilibrium is established between the adsorption and desorption of gas molecules on the adsorbent material. Adsorption of gas molecules can be caused by steric, kinetic or equilibrium effects. The exact mechanism will be determined by the adsorbent used and the equilibrium saturation will depend on the temperature and pressure. Typically, the adsorbent material is treated in a mixed gas until the heaviest compounds are near saturation, and then regeneration is required. Regeneration may be accomplished by varying the pressure or temperature. In practice this means that a process is used with at least two units, first saturating the adsorbent in one unit at high or low pressure, then switching the units and now desorbing the adsorbed molecules from the same unit by lowering the pressure or raising the temperature. When the unit is operated under pressure changes it is referred to as a pressure swing adsorption unit and when the unit is operated under temperature changes it is referred to as a temperature swing adsorption unit. Pressure swing adsorption can produce hydrogen purity of 99.9% or greater. Membrane refers to separation on an at least partially solid barrier (e.g., a polymer) where transport of individual gaseous species occurs at different rates defined by their permeability. This allows for the enhancement or dilution of the components in the membrane retentate. Cryogenic separation refers to the process of separating individual components from a gas mixture by controlling the temperature using phase changes of different substances in the gas, which typically occurs below-150 ℃. It should be noted that the gas separation unit also potentially provides a by-product stream, e.g. from CO 2Removing CO of operation2And (4) streaming.
In one embodiment, the downstream section comprises an ammonia reactor to convert the intermediate syngas to ammonia. In another embodiment, the downstream section comprises a methanol reactor to convert the intermediate syngas to methanol. In yet another embodiment, the downstream section comprises a fischer-tropsch reactor to convert the intermediate synthesis gas to a mixture of higher hydrocarbons.
In one embodiment, the first, second, third, fourth, fifth and/or sixth catalyst is a catalyst suitable for steam reforming reactions, pre-reforming reactions, methanation and/or water gas shift reactions. An example of such a catalyst of interest is Ni/MgAl2O4、Ni/CaAl2O4、Ni/Al2O3、Fe2O3/Cr2O3MgO and Cu/Zn/Al2O3. In one embodiment, the first, second, third, fourth, fifth and/or sixth catalyst is a steam reforming catalyst. An example of a steam reforming catalyst is Ni/MgAl2O4、Ni/Al2O3、Ni/CaAl2O4、Ru/MgAl2O4、Rh/MgAl2O4、Ir/MgAl2O4、Mo2C、Wo2C、CeO2、Al2O3Noble metals on a carrier, but other catalysts suitable for reforming are also conceivable.
Another aspect of the invention relates to a method for producing a chemical product from a feed gas comprising hydrocarbons in a chemical plant comprising a reforming section. The reforming section includes an electrically heated reforming reactor containing a first catalyst, an autothermal reforming reactor in parallel with the electrically heated reforming reactor. The autothermal reforming reactor contains a second catalyst. The method comprises the following steps:
-introducing a first portion of the feed gas into an electrically heated reforming reactor and performing steam methane reforming to provide a first synthesis gas stream,
-introducing a second portion of the feed gas into the autothermal reforming reactor and reforming to provide a second synthesis gas stream,
-outputting from the reforming section a combined syngas stream comprising at least part of the first and/or second syngas stream,
-optionally post-treating the combined synthesis gas stream in a post-treatment unit downstream of the electrically heated reforming reactor and the autothermal reforming reactor to provide a post-treated synthesis gas stream,
-separating the combined synthesis gas stream or the post-treated synthesis gas stream into a water condensate and an intermediate synthesis gas in a water separation unit downstream of the post-treatment unit, and
-feeding the intermediate syngas to a downstream section arranged to receive the intermediate syngas and process the intermediate syngas into chemical products and off-gas.
The advantages of the method and its embodiments correspond to those of the chemical plant and its embodiments and are therefore not described in further detail here.
It should be noted, however, that the first, second and optional third portions of the hydrocarbon-containing feed gas may be first, second and optional third portions of a single hydrocarbon-containing feed gas stream, wherein the single feed gas stream is divided into a plurality of streams that may be fed with steam to the first, second and optional third reforming reactors. In this case, the composition of the first portion, the second portion and the optional third portion of the feed gas is substantially the same. However, additional gases (e.g., oxidant gas and/or steam) may be added to the first, second and optional third portions of the feed gas before they are fed into the respective reforming reactors.
In one embodiment, the first portion of the feed gas is about 5 to 20 volume percent of the feed gas. In case the reforming section comprises an electrically heated reforming reactor and a combustion reforming reactor and no further reactors, the first portion of the feed gas entering the electrically heated reforming reactor is advantageously about 10-20 vol%, such as about 15 vol%, of the feed gas and thus the second portion of the feed gas entering the autothermal reforming reactor is about 80-90 vol%, such as about 85 vol%, of the feed gas.
In one embodiment, wherein the reforming section comprises a gas-heated steam methane reforming reactor, the first portion of the feed gas is about 5-10 vol% of the feed gas, the second portion of the feed gas is about 80-90 vol% of the feed gas, and the third portion of the feed gas is about 5-10 vol% of the feed gas.
Further, it should be noted that the order in which process steps are written is not necessarily the order in which the process steps occur, as two or more steps may occur simultaneously, or the order may be different than that described above.
Brief description of the drawings
FIG. 1 shows a chemical plant in which a reforming section comprises an autothermal reforming reactor and an electrically heated reforming reactor in parallel, according to one embodiment of the invention;
FIG. 2 shows a chemical gas plant according to one embodiment of the invention in which the reforming section further comprises a fired steam methane reforming reactor upstream of the autothermal reforming reactor; and
figure 3 shows a chemical plant in which the reforming section comprises four reforming reactors, according to one embodiment of the present invention.
Fig. 4 shows a chemical gas plant according to one embodiment of the invention in which the reforming section further comprises a gas heated steam methane reforming reactor upstream of the autothermal reforming reactor.
Detailed Description
FIG. 1 shows a chemical plant 100 according to one embodiment of the invention. The chemical plant 100 includes a reforming section 110 having an autothermal reforming reactor 109 and an electrically heated reforming reactor 108 in parallel.
The electrically heated reforming reactor 108 contains a first catalyst and the autothermal reforming reactor 109 contains a second catalyst. The electrically heated reforming reactor 108 is heated by a power supply 107.
The electrically heated reforming reactor 108 and the autothermal reforming reactor 109 are arranged in parallel. The electrically heated reforming reactor 108 is heated by a power supply 107. The electrically heated reforming reactor 108 and the autothermal reforming reactor 109 are arranged to receive the first portion 25a and the second portion 25b of the feed gas 25 and to produce a first syngas 30a and a second syngas 30b, respectively.
During operation of the chemical plant 100, the feed gas 21 comprising hydrocarbons undergoes feed cleanup in the desulfurization unit 101 and becomes a desulfurized gas 22. The feed gas 21 comprising hydrocarbons is, for example, natural gas or town gas. The sweetened gas 22 is preheated in the combustion heating unit 105 and steam 23 is added to the sweetened gas 22, producing a stream 24. The gas stream 24 is directed to a pre-reforming unit 102 containing a steam reforming catalyst. Typically, the pre-reforming unit 102 is an adiabatic pre-reforming unit in which the higher hydrocarbons react such that the pre-reformed gas 25 exiting the pre-reforming unit 102 contains no or very little higher hydrocarbons. The pre-reformed gas 25 is split into a first portion 25a of the feed gas to the electrically heated reforming reactor 108 and a second portion 25b of the feed gas to the autothermal reforming reactor 109. Additional steam may be added to the first portion 25a of the feed gas (not shown in fig. 1). The first catalyst in the electrically heated reforming reactor 108 is a steam methane reforming catalyst arranged to catalyse the steam methane reforming reaction in the electrically heated reforming reactor 108. The autothermal reforming reactor 109 also includes a steam methane reforming catalyst arranged to perform a steam methane reforming reaction. Air or oxygen 26 is also added to the autothermal reforming reactor 26 to cause partial combustion of the second portion 25b of the feed gas to occur upstream of the second catalyst in the autothermal reforming reactor 109. The first syngas stream 30a and the second syngas stream 30b exit the electrically heated reforming reactor 108 and the autothermal reforming reactor 109, respectively, and are combined into a combined syngas stream 30 that exits the reforming section 110. The combined syngas stream 30 is cooled in heat exchanger 111 to form a cooled combined syngas stream 30'. The cooled combined syngas stream 30' enters a post-treatment unit 112, i.e., a water gas shift unit, and the water gas shifted syngas 32 exits the water gas shift unit 112. The water gas shift synthesis gas 32 is cooled in the second heat exchanger 113 to a cooled water gas shift synthesis gas 32 'which enters a water separation unit 115, such as a flash separation unit 115, which is arranged to separate the cooled water gas shift synthesis gas 32' into a condensate 27 and an intermediate synthesis gas 34. The intermediate syngas 34 is dry syngas and enters the downstream section 116, which downstream section 116 is arranged to process the syngas 34 into the chemical product 40 and the off-gas 45. The downstream section 116 includes, for example, an ammonia reactor to convert the intermediate syngas 34 to ammonia, a methanol reactor to convert the intermediate syngas 34 to methanol, or a fischer-tropsch reactor to convert the intermediate syngas 34 to a higher hydrocarbon mixture.
The exhaust gas 45 from the downstream section 116 is recirculated as fuel to one or more burners of the fired heating unit 105. The exhaust gas 45 is combined with a small amount of natural gas 46 to form a fuel gas 47, which fuel gas 47 is sent to one or more burners of the fired heating unit 105. The combustion heating unit is arranged to provide heat to preheat the feed gas 21, the desulphurised feed gas 22 and the first portion 25a and/or the second portion 25b of the feed gas 25. In fig. 1, only the second portion 25b of the feed gas 25 is heated in the combustion heating unit 105 prior to entering the autothermal reforming reactor 109. However, it is also conceivable that the first portion 25a of the feed gas 25 is preheated in the combustion heating unit 105.
Heat exchange fluid 20 (e.g., water) is used for heat exchange in heat exchanger 111, and the heated heat exchange fluid (e.g., steam) is output as stream 20'. A portion of the steam is used as steam 23 added to the desulfurized gas 22.
It should be noted that the chemical plant 100 typically includes other equipment, such as compressors, heat exchangers, etc.; however, such other devices are not shown in fig. 1.
Fig. 2 shows a chemical gas plant 200 according to an embodiment of the invention, wherein the reforming section 210 further comprises a combustion steam methane reforming reactor 104 upstream of the autothermal reforming reactor 109.
The chemical plant 200 includes a reforming section 210 having an electrically heated reforming reactor 208 containing a first catalyst, an autothermal reforming reactor 109 containing a second catalyst, and a fired steam methane reforming reactor 104 containing a third catalyst. The combustion reforming reactor 104 is a side-fired tubular steam methane reforming reactor 104. Thus, the side-fired tubular steam methane reforming reactor 104 comprises a plurality of tubes 106 containing the third catalyst and a plurality of burners 103 arranged to heat the tubes 106. For clarity, only one tube 106 is shown in FIG. 2. Fuel is supplied to burner 103 and combusted to provide heat for tube 106. Hot flue gas from the combustor 103 is directed to the preheating section 205 of the steam methane reforming reactor 104 and used to preheat the feed gas and steam. The electrically heated reforming reactor 108 is arranged in parallel with the combination of the fired steam methane reforming reactor 104 and the autothermal reforming reactor 109. The electrically heated reforming reactor 108 is heated by a power supply 107.
The electrically heated reforming reactor 108 and the side-fired steam reforming reactor 104 are arranged to receive the first feed gas 25a and the second feed gas 25b, respectively, and produce a first syngas 30a and a pre-reformed feed gas 25 b. The pre-reforming feed gas 25b leaves the combustion reforming reactor at a temperature between 700 ℃ and 900 ℃ and therefore does not require further preheating before entering the autothermal reforming reactor 109. An air or oxygen stream 26 is fed to the autothermal reforming reactor 109. The autothermal reforming reactor 109 outputs the second syngas 30 b.
During operation of the chemical plant 200, the feed gas 21 comprising hydrocarbons undergoes feed cleanup in the desulfurization unit 101 and becomes a desulfurized gas 22. The feed gas 21 comprising hydrocarbons is, for example, natural gas or town gas. The sweetened gas 22 is preheated in preheat section 205 of steam methane reformer 104 and steam 23 is added to produce gas stream 24. The gas stream 24 is directed to a pre-reforming unit 102 containing a steam reforming catalyst. Typically, the pre-reforming unit 102 is an adiabatic pre-reforming unit in which the higher hydrocarbons react such that the pre-reformed gas 25 exiting the pre-reformer contains no or very little higher hydrocarbons. The pre-reformed gas 25 is split into a first portion 25a of the feed gas to the electrically heated reforming reactor 208 and a second portion 25b of the feed gas to the steam methane reformer 104. The first catalyst in the electrically heated reforming reactor 108, the second catalyst in the autothermal reforming reactor 109 and the third catalyst in the steam methane reformer 104 are steam methane reforming catalysts arranged to catalyse the steam methane reforming reactions in the electrically heated reforming reactor 108, the steam methane reformer 104 and the autothermal reforming reactor 109.
The electrically heated reforming reactor 108 produces a first syngas 30a, the steam methane reformer 104 produces a partially reformed syngas 25b, and the autothermal reforming reactor 109 provides a second syngas 30 b. The first syngas 30a and the second syngas 30b are combined into a syngas stream 30, which is output from the reforming section 210 as the combined syngas stream 30.
The combined syngas stream 30 is cooled in heat exchanger 111 to form a cooled combined syngas stream 30'. The cooled combined syngas stream 30' enters the post-treatment unit 112, i.e., a water gas shift unit, and the water gas shifted syngas 32 exits the water gas shift unit 212. The water gas shift syngas 32 is cooled in a second heat exchanger 113 to a cooled water gas shift syngas 32' which enters a water separation unit 114, such as a flash separation unit 115. The cooled water gas shift syngas 32' is separated into a condensate 27 and an intermediate syngas 34. The intermediate syngas 34 is dry syngas that is channeled to the downstream section 116, the downstream section 116 is arranged to process the intermediate syngas 34 into the chemical products 40 and the off-gas 45.
The downstream section 116 includes, for example, an ammonia reactor to convert the intermediate syngas 34 to ammonia, a methanol reactor to convert the intermediate syngas 34 to methanol, or a fischer-tropsch reactor to convert the intermediate syngas 34 to a higher hydrocarbon mixture.
The exhaust gas 45 from the downstream section 116 is recycled as fuel to the combustor 103 of the steam methane reformer 104. The flue gas 45 is combined with a small amount of natural gas 46 to form a fuel gas 47 that is sent to the combustor 103 of the steam methane reformer 104. The fuel gas 47 is burned in the burner 103, thereby heating the tubes 106 with the third catalyst. In the preheating section 205, the flue gas from the burner 103 provides heat for preheating the feed gas and is discharged from the preheating section 205 as flue gas 48. Heat exchange fluid 20 (e.g., water) is used for heat exchange in heat exchanger 211 and the heated heat exchange fluid (e.g., steam) is output as stream 20'. A portion of the steam is used as steam 23 added to the presulfiding gas 22.
It should be noted that the chemical plant 200 typically includes other equipment, such as compressors, heat exchangers, etc.; however, such other devices are not shown in fig. 2.
Fig. 3 shows a chemical plant 300 according to an embodiment of the invention, wherein the reforming section comprises four reforming reactors (i.e. an electrically heated reforming reactor 108 containing a first catalyst in parallel with a combination of a steam fired reforming reactor 104 containing a third catalyst and an autothermal reactor 109 containing a second catalyst), and also a gas heated reactor 112 containing a fourth catalyst.
The combustion steam reforming reactor 104 is a side-fired tubular steam methane reforming reactor 104 comprising a plurality of tubes 106 containing a third catalyst and a plurality of burners 103 arranged to heat the tubes 106. For clarity, only one tube is shown in FIG. 3. Fuel is supplied to burner 103 and combusted to provide heat for tube 106. The hot flue gas from the combustor 103 is directed to the preheating section 205 of the steam methane reforming reactor 104 and used to preheat the feed gas and steam. The electrically heated reforming reactor 108 is arranged in parallel with the combination of the upstream fired steam reforming reactor 104 and the autothermal reforming reactor 109. The electrically heated reforming reactor 108 is heated by a power supply 107.
A first portion 25a of the hydrocarbon-containing feed gas 25 is directed to the electrically heated reforming reactor 108 and a second portion 25b of the hydrocarbon-containing feed gas 25 is directed to the side-fired steam reforming reactor 104. In the side-fired steam reforming reactor 104, a second portion 25b of the feed gas 25 is partially reformed into a partially reformed second feed gas 25b, which is fed with a stream 26 of oxidant gas (e.g., oxygen or air) to the autothermal reforming reactor 109.
During operation of the chemical plant 300, the feed gas 21 comprising hydrocarbons undergoes feed purification in the desulfurization unit 101 and becomes a desulfurized gas 22. The feed gas 21 comprising hydrocarbons is, for example, natural gas or town gas. The sweetened gas 22 is preheated in the preheating section 205 of the steam methane reforming reactor 104 and steam 23 is added to produce the gas stream 24. The gas stream 24 is directed to a pre-reforming unit 102 containing a steam reforming catalyst. Typically, the pre-reforming unit 102 is an adiabatic pre-reforming unit in which the higher hydrocarbons react such that the pre-reformed gas 25 exiting the pre-reformer contains no or very little higher hydrocarbons. The pre-reformed gas 25 is split into a first portion 25a of the feed gas to the electrically heated reforming reactor 108, a second portion 25b of the feed gas to the fired steam methane reforming reactor 104 and a third portion 25c of the feed gas to the gas heated steam methane reforming reactor 112.
The first catalyst in the electrically heated reforming reactor 308, the second catalyst in the autothermal reformer 109, the third catalyst in the steam methane reforming reactor 104 and the fourth catalyst in the gas-heated steam methane reforming reactor 112 are steam methane reforming catalysts arranged to catalyze steam methane reforming reactions carried out in the electrically heated reforming reactor 108, the autothermal reformer 109, the steam methane reforming reactor 104 and the gas-heated steam methane reforming reactor 112.
The first, second and third portions 25a, 25b, 25c of the feed gas 25 are subjected to steam methane reforming in an electrically heated reforming reactor 108, a steam methane reforming reactor 104, an autothermal reforming reactor 109 and a gas heated steam methane reforming reactor 106, respectively. The electrically heated reforming reactor 108 produces a first syngas 30a, while the steam methane reforming reactor 104 produces a partially reformed second feed gas 25b', which is further reformed in an autothermal reforming reactor 109 to provide a second syngas 30 b. The first synthesis gas 30a and the second synthesis gas 30b are combined into a synthesis gas stream 31, which synthesis gas stream 31 is fed to the gas heated steam methane reforming reactor 112 to provide heat for the steam methane reforming reaction of the third portion 25c of the feed gas entering the gas heated steam methane reforming reactor 112 from the other side.
The syngas stream 30 exits the gas-heated steam methane reforming reactor 112 and is thereby discharged from the reforming section 310 as a combined syngas stream 30. The combined syngas stream 30 is cooled in heat exchanger 113 to a cooled combined syngas stream 30'.
The cooled combined syngas stream 30 'enters a water separation unit 114, such as a flash separation unit 115, which is arranged to separate the cooled combined syngas 30' into a condensate 27 and an intermediate syngas 34 in the form of dry syngas. The dry syngas 34 enters the downstream section 116, which is arranged to process the dry syngas 34 into the chemical products 40 and the off-gas 45. The downstream section 116 includes, for example, an ammonia reactor to convert the intermediate syngas 34 to ammonia, a methanol reactor to convert the intermediate syngas 34 to methanol, or a fischer-tropsch reactor to convert the intermediate syngas 34 to a higher hydrocarbon mixture.
The exhaust gas 45 from the downstream section 116 is recycled as fuel to the combustor 103 that burns the steam methane reforming reactor 104. The off-gas 45 is combined with a small amount of natural gas 46 to form a fuel gas 47 which is sent to the combustor 103 of the steam methane reforming reactor 104. The fuel gas 47 is burned in the burner 103, thereby heating the tubes 106 with the third catalyst. In the preheating section 305, the flue gas from the combustor 103 provides heat for preheating the feed gas and is discharged from the preheating section 305 as flue gas 48. Heat exchange fluid 20 (e.g., water) is used for heat exchange in heat exchanger 113, and the heated heat exchange fluid (e.g., steam) is output as stream 20'.
It should be noted that the chemical plant 300 typically includes other equipment, such as compressors, heat exchangers, etc.; however, such other devices are not shown in fig. 3.
Fig. 4 shows a chemical gas plant 400 according to one embodiment of the invention, wherein the reforming section 410 further comprises a gas steam methane reforming reactor 420 upstream of the autothermal reforming reactor 109.
The second portion 25b of the feed gas is heated and pre-reformed in the gas steam methane reforming reactor 420 to provide a partially reformed second feed gas 25c, and the partially reformed second feed gas 25c is directed to the autothermal reforming reactor 109. The second syngas 30b is used as a heating medium for heat exchange within the gas heated steam methane reforming reactor 420 to heat the second portion 25b of the feed gas to provide a partially cooled second syngas 30 c. The partially cooled second syngas 30c is combined with the first syngas 30a to form the combined syngas 30 exiting the reforming section 410.
Example 1
Table 1 shows one example of how an ATR and an electric reformer can be integrated to produce a combined syngas. First, by connecting the electrical reformer in parallel with the ATR, the syngas production capacity is increased without additional increase in oxygen requirements. Secondly, the modulus of the syngas can be varied, since the H outside the ATR 2The ratio of/CO is 2.3, which in the given case is the sum ofAnd the syngas was increased to 2.6.
TABLE 1
Figure BDA0003228655380000251

Claims (25)

1. A chemical plant, comprising:
-a reforming section arranged to receive a feed gas comprising hydrocarbons and to provide a combined synthesis gas stream, wherein the reforming section comprises:
-an electrically heated reforming reactor containing a first catalyst, the electrically heated reforming reactor being arranged to receive a first portion of the feed gas and to produce a first synthesis gas stream,
-an autothermal reforming reactor in parallel with the electrically heated reforming reactor, the autothermal reforming reactor containing a second catalyst, the autothermal reforming reactor being arranged to receive a second portion of the feed gas and to output a second synthesis gas stream,
wherein the reforming section is arranged to output a combined syngas stream comprising at least a portion of the first and/or second syngas streams,
-an optional post-treatment unit downstream of the reforming section, wherein the optional post-treatment unit is arranged to receive the combined syngas stream and to provide a post-treated syngas stream,
-a water separation unit arranged to separate the combined syngas stream or the post-treated syngas stream into a water condensate and an intermediate syngas, and
-a downstream section arranged to receive the intermediate syngas and process the intermediate syngas into chemical products and off-gas.
2. The chemical plant of claim 1, wherein the electrically heated reforming reactor comprises:
-a pressure shell containing an electrical heating unit arranged to heat the first catalyst, wherein the first catalyst comprises a catalytically active material operable to catalyze the steam reforming of the first portion of the feed gas, wherein the pressure shell has a design pressure of 5 to 45 bar, preferably 30 to 45 bar,
-a thermal insulation layer adjacent to at least a portion of the interior of the pressure shell, and
-at least two conductors electrically connected to the electrical heating unit and to a power source placed outside the pressure shell,
wherein the power source is dimensioned to heat at least a portion of the first catalyst to a temperature of at least 800 ℃, preferably at least 950 ℃, or even more preferably at least 1050 ℃, by passing an electric current through the electrical heating unit.
3. The chemical plant of claim 2, wherein the electrical heating unit comprises a macrostructure of electrically conductive material, wherein the macrostructure supports a ceramic coating and the ceramic coating supports the catalytically active material.
4. The chemical plant of any one of claims 1 to 3, further comprising:
-a combustion heater unit upstream of the autothermal reforming reactor, the combustion heater unit being arranged to preheat the second portion of the feed gas, and
-means for recirculating at least part of the exhaust gas from the downstream section as fuel to a fired heater unit.
5. The chemical plant of any one of claims 1 to 3, wherein the reforming section further comprises a steam-fired methane reforming reactor located upstream of the autothermal reforming reactor, wherein the steam-fired methane reforming reactor comprises one or more tubes containing a third catalyst; wherein the combustion steam methane reforming reactor comprises one or more burners for providing heat for the steam methane reforming reaction within the one or more tubes; and wherein the chemical plant comprises one or more burners for recycling at least part of the off-gas from the downstream section as fuel to a fired steam methane reforming reactor; wherein the combustion steam methane reforming reactor is arranged to receive the second portion of the feed gas and to provide a partially reformed second feed gas; and wherein the partially reformed second feed gas is introduced into the autothermal reforming reactor.
6. The chemical plant of any one of claims 1 to 5 wherein the reforming section further comprises a gas-heated steam methane reforming reactor in parallel with the combination of the electrically-heated steam methane reforming reactor and the autothermal reforming reactor, wherein the gas-heated steam methane reforming reactor comprises a fourth catalyst and is operable to receive a third portion of the feed gas and to utilise at least a portion of the first and/or second synthesis gas stream as a heating medium in heat exchange within the gas-heated steam methane reforming reactor, the gas-heated steam methane reforming reactor being arranged to produce a third synthesis gas stream and to output the third synthesis gas stream from the reforming section as at least a portion of the combined synthesis gas stream.
7. The chemical plant of any one of claims 1 to 5 wherein the reforming section further comprises a gas-heated steam methane reforming reactor located upstream of the autothermal reforming reactor, wherein the gas-heated steam methane reforming reactor contains a fourth catalyst and is operable to utilise at least part of the second synthesis gas stream as a heating medium in heat exchange within the gas-heated steam methane reforming reactor, the gas-heated steam methane reforming reactor being arranged to receive the second portion of the feed gas and to provide a partially reformed second feed gas, wherein the partially reformed second feed gas is introduced into the autothermal reforming reactor.
8. The chemical plant of claim 7, wherein the gas-heated steam methane reforming reactor is further operable to utilize at least a portion of the first syngas stream as a heating medium in heat exchange within the gas-heated steam methane reforming reactor.
9. The chemical plant according to any of claims 1 to 8, wherein the post-treatment unit is a post-conversion unit having CO allowing heating2An inlet added to the combined syngas stream upstream of the post-reforming unit and containing a fifth catalyst active to catalyze steam methane reforming, methanation, and reverse water gas shift.
10. The chemical plant of any one of claims 1 to 9, wherein the post-treatment unit is a water gas shift unit arranged to perform a water gas shift reaction.
11. The chemical plant of any one of claims 1 to 10 wherein the downstream section comprises a gas separation unit arranged to separate substantially pure CO from the intermediate syngas2、H2And/or a stream of CO to provide a refined synthesis gas.
12. The chemical plant according to any one of claims 1 to 11, wherein the downstream section comprises an ammonia reactor for converting the intermediate synthesis gas or the refined synthesis gas into ammonia, a methanol reactor for converting the intermediate synthesis gas or the refined synthesis gas into methanol, or a fischer-tropsch reactor for converting the intermediate synthesis gas or the refined synthesis gas into a mixture of higher hydrocarbons.
13. A process for producing a chemical product from a feed gas comprising hydrocarbons in a chemical plant comprising a reforming section comprising an electrically heated reforming reactor containing a first catalyst, an autothermal reforming reactor in parallel with the electrically heated reforming reactor containing a second catalyst, the process comprising the steps of:
-introducing a first portion of the feed gas into the electrically heated reforming reactor and performing steam methane reforming to provide a first synthesis gas stream,
-introducing a second portion of the feed gas into the autothermal reforming reactor and reforming to provide a second synthesis gas stream,
-outputting from the reforming section a combined syngas stream comprising at least part of the first and/or second syngas stream,
-optionally post-treating the combined syngas stream in a post-treatment unit downstream of the electrically heated reforming reactor and the autothermal reforming reactor to provide a post-treated syngas stream,
-separating the combined syngas stream or the post-treated syngas stream into a water condensate and an intermediate syngas in a water separation unit downstream of the post-treatment unit, and
-feeding said intermediate syngas to a downstream section arranged to receive and process the intermediate syngas into chemical products and off-gas.
14. The process of claim 12, wherein the electrically heated reforming reactor comprises a pressure shell containing an electrical heating unit arranged to heat the first catalyst, wherein the first catalyst comprises a catalytically active material operable to catalyze the steam reforming of the first portion of the feed gas, wherein the pressure shell has a design pressure of 5 to 45 bar;
-a thermal insulation layer adjacent to at least a portion of the interior of the pressure shell, and
-at least two conductors electrically connected to the electrical heating unit and to a power source placed outside the pressure shell,
wherein the method further comprises the steps of:
-pressurizing the first portion of the feed gas to a pressure of 5 to 45 bar, preferably 30 to 45 bar, upstream of the electrically heated reforming reactor,
-passing an electric current through the electrical heating unit, thereby heating at least a portion of the first catalyst to a temperature of at least 800 ℃, preferably at least 950 ℃, or even more preferably at least 1050 ℃.
15. The method of claim 13 or 14, further comprising:
-supplying fuel to a combustion heater unit upstream of the autothermal reforming reactor, thereby preheating the second portion of the feed gas, and
-recirculating at least part of the exhaust gas from the downstream section as fuel to the fired heater unit.
16. The process of any one of claims 13 or 14, wherein the reforming section further comprises a steam fired methane reforming reactor upstream of the autothermal reforming reactor; wherein the steam methane reforming reactor comprises one or more tubes containing a third catalyst; wherein the combustion steam methane reforming reactor comprises one or more burners for providing heat for the steam methane reforming reaction within the one or more tubes; the method further comprises the steps of:
-introducing said second portion of feed gas into said combustion steam methane reforming reactor and performing steam methane reforming within the tubes of said combustion reforming reactor to provide a partially reformed second feed gas,
-providing the partially reformed second feed gas to the autothermal reforming reactor, and
-recycling at least part of the exhaust gas from the downstream section as fuel to one or more burners of a fired steam methane reforming reactor.
17. The process of any one of claims 13 to 16, wherein the reforming section further comprises a gas-heated steam methane reforming reactor in parallel with the combination of the electrically-heated reforming reactor and the autothermal reforming reactor, wherein the gas-heated steam methane reforming reactor comprises a fourth catalyst, the process further comprising the steps of:
-introducing a third portion of the feed gas into the gas-heated steam methane reforming reactor,
-using at least part of the first and/or second synthesis gas stream as a heating medium in heat exchange in the gas heated steam methane reforming reactor,
-producing a third synthesis gas stream by means of a fourth catalyst in a gas-heated steam methane reforming reactor, and
-outputting the third syngas stream from the reforming section as at least a portion of the combined syngas.
18. The process of claim 13 or 14, wherein the reforming section further comprises a gas heated steam methane reforming reactor upstream of the autothermal reforming reactor, wherein the gas heated steam methane reforming reactor contains a fourth catalyst, the process further comprising the steps of:
-introducing said second portion of feed gas into said gas heated steam methane reforming reactor and performing steam methane reforming within said combustion reforming reactor to provide a partially reformed second feed gas,
-providing the partially reformed second feed gas to the autothermal reforming reactor, and
-using at least part of the second synthesis gas stream as a heating medium in heat exchange in the gas heated steam methane reforming reactor.
19. The method of claim 18, further comprising the steps of:
utilizing at least a portion of the first syngas stream as a heating medium in heat exchange within the gas-heated steam methane reforming reactor.
20. The method of any one of claims 13-19, wherein the post-treatment unit is a post-conversion unit containing a fifth catalyst active to catalyze steam methane reforming, methanation, and reverse water gas shift reactions, wherein the method further comprises passing the heated CO2A step of introducing into the combined synthesis gas stream upstream of the post-conversion unit.
21. The method of any one of claims 13 to 20, wherein the post-treatment unit is a water gas shift unit and the step of post-treating the combined syngas stream comprises performing a water gas shift reaction.
22. The method of any one of claims 13 to 21, wherein the method comprises separating substantially pure CO from the intermediate syngas2、H2And/or CO, to provide a refined synthesis gas in the one or more gas separation units of the downstream section.
23. The process of any one of claims 13 to 22, wherein the first portion of the feed gas is about 5-20 vol% of the feed gas.
24. The method of claim 17, wherein the first portion of the feed gas is about 5-10 vol% of the feed gas and the third portion of the feed gas is about 5-10 vol% of the feed gas.
25. The method of any one of claims 13 to 24, wherein the method further comprises: converting the intermediate synthesis gas to ammonia in an ammonia reactor of the downstream section, to methanol in a methanol reactor of the downstream section, or to a mixture of higher hydrocarbons in a fischer-tropsch reactor.
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